Compositions containing substituted alkyl halides



I Patented Sept. 5, 1944 I OOMPOSITIONS CONTAINING SUBSTITUTED ALKYLHALIDES Gaetanfl F. Dunno, runn rs, Mass assignor to General ElectricCompany, a corporation of New York No Drawing. Application February 27,1942,

Serial No. 432.658

20 Claims.

This invention relates to the production of new materials and moreparticularly is concerned with synthetic compositions of particularutility in the plastics and coating arts and which contain, or areproduced from, certain substituted alkyl halides hereafter identified.This application is a continuation-in-part of my copending applicationSerial No. 417,505, filed November l, 1941, now Patent No. 2,312,693,and assigned ,to the same assignee as the present invention.

The substituted alkyl halides used in carrying the present inventioninto eflect may be represented by the following general formula:

' ll RHNSOr-Y-NR-C Cn Rin where n represents an integer and is at least1 and not more than 2, Z represents a member of the class consisting ofoxygen and sulfur, Y represents a divalent carboxylic radical, R repre-'sents a member of the class consisting of hydrogen and monovalenthydrocarbon and substituted hydrocarbon radicals, more particularlyhalo-hydrocarbon radicals, and X represents a halogen atom, moreparticularly a chlorine, bromine, fluorine or iodine atom. Since nrepresents an integer which is 1 or 2, it will be seen that the halogenatom represented by X in all cases will be alpha or beta to the carbamylor thiocarbamyl grouping.

Illustrative examples of radicals that R in the above formula mayrepresent are: aliphatic (e. 3., methyl, ethyl, propyl, isopropyl,allyl, butyl, secondary butyl, isobutyl, amyl, isoamyl, hexyl,methallyl, ethallyl, crotyl, etc), including cycio aliphatic (e. g.,cyclopentyl, cyclopentenyl, cy clohexyl, cyclohexenyl, cycloheptyl,etc); aryl (e. g., phenyl, diphenyl or xenyi, naphthyl, etc.)aliphatic-substituted aryl (e. g., tolyl, xylyl, ethylphenyl,propylpnenyl, isopropylphenyl, aIlylphenyl, Z-butenylphenyl,tertiary-butylphenyl,

for instance,;'as those represented by the formulas:

z RHNSOr-Y-N R(")-C nHln and, more particularly,

m HzNSO:YNH(J-CH1C1 where n, Z, Y, R and K have the same meanings asabove given with reference to Formula I.

Illustrative examples of divalent carbocyclic radicals that Y inFormulas I, II and III may represent are: arylene, e. g., phenylene,xenylene, naphthylene, etc.; alkarylene, e. g., 1,4-t0lylene,para-(2,3-xylylene) etc.; cycloalkylene, e. g., cycyclopentylene,cyclohexylene, etc.; cycloalkenylene, e. g., cyclopentenylene,cyclohexenylene, etc.; and their homologues, as well as those divalentcarbocyclic radicals with one or more of their hydrogen atoms replacedby a substituent,

e. g.,. halogeno, amino, acetyl, acetoxy, carboalkoxy, allroxy aryloxy,hydroxy, alkyl, alkenyl, an --SO2NHR. group in addition to the single-SO2NHR group shown in the above formulas, etc. Specific examples ofsubstituted divalent carbocyclic radicals are chlorophenylene,bromophenylene, bromonaphthylene, bromo 1,4-tolylene,chlorocyclopentylene, bromocyclopentenyla ene, carbomethoxyphenylene,ethoxyphenylene. acetophenylene, ac'etoxyphenylene, bromocyclopentylene,aminophenylene, phenoxyphenylene, hydroxyphenylene, methylphenylene(toiylene), allylphenylene, etc.' Preferably Y is phenylene ormethylphenylene.

The substituted alkyl halides used in carrying the present inventioninto effect may be produced in various ways. One suitable methodcomprises etc); aryl-substituted aliphatic, (e. g., benwl,

by the following general equation:

hydrohalide acceptor acceptor where a, Z Y, R and X have the samemeanings as above given with reference to Formula I.

Specific examples of substituted allwl halides embraced by Formula Ithat may be used in carrying the present invention into effect arelisted below:

Ortho -sulfamyl phenyl carbamyi chloro methaneMeta-suliamyl-phenyl-carbamyl chloro methane Ortho sultamyl phenylthiocarbamyl chloro methane Meta suliamyl phenyl thiocarbamyl chloromethane Para sulfamyl phenyl thiocarbamyl chloro methaneOrtho-suli'amyl-tolyl-carbamyl chloro methanePara-sulfamyl-tolyl-carbamyl chloro methane Meta-sulfamyl-tolyl-carbamylchloro methane Ortho-sulfamyl-tolyl-thiocarbamyl bromo methane Orthosulfamyl phenyl -thiocarbamyl bromo methane Para sulfamyl tolylthiocarbamyl bromo methane Para-sulfamyl-tolyl-carbamyi bromo methanePara suliamyl phenyl thiocarbamyl bromo methanePara-sulfamyl-phenyl-carbamyl chloro methane Alpha-(para-sulfamyl-phenylcarbamyl) betachloro ethane Alpha-(meta-sulfamyl-pheny1-carbamy1)alphachloro ethane Alpha [para- (sulfonyl methylamide)phenylthiocarbamyl] alpha-chloro pentane Ortho sulfamyl phenyl (methyl)carbamyl bromo methane Alpha- (4 suliamyl naphthyl [1] carbamyl)beta-chloro 3-butene Alpha -(para-sulfamyl-chlorophenyl carbamyl)alpha-ethyl beta-phenyl beta-bromo ethane Para-(sulfonyl pentylamide)-tolyl-carbamyl cyclopentyl chloro methane Para (sulfonyl 3butenylamide) chlorotolyl- (butyl) -carbamyl bromo methane Para-(sulfonyl cyclohexylamide) -phenyl- (cyclopentyl) -thiocarbamyl chloromethane Parasulfonyl phenylamide) phenyl (chloroethyl)-carbamyl bromomethane 4- (sulfonyl chlorotolylamide) -cyclohexy1- (phenyl) -carbamylchloro methane 3-sulfamyl-cyclopentyl carbamyl tolyl chloro methaneAlpha [para (sulfonyl propylphenylamide)- phenyl-(bromo phenyl)-thiocarbamyll betachloro ethane Alpha- [para- (sulfonylphenylchloroethylamide) phenyl-(xenyl) -carbamyll alpha chlorotolylbeta-chloro ethane Qrtho- (sulfonyl chloroethylamide) phenyl-carbamylchloro methane Meta (sulfonyl naphthylamide) phenyl carbamyl iodomethane Para-suli'amyl-phenyl-carbamyl alpha-(bromophenyl) beta-chloroethane Para (sulfonyl isobutylphenylamide) phenylcarbamyl naphthylchloro methane Para-sulfamyl-phenyl-carbamyl iodo methaneOrtho-sulfamy1-phenyl-carbamyl fluoro methane Alpha (meta sulfamyl tolylthiocarbamyl) beta-bromo ethane Alpha- (ortho-sulfamy1-phenyl-carbamyl)bromo ethane Ortho-sulfamyl-phenyl-carbamyl iodo methane Para sulfamylchlorophenyl carbamyl chloro methane beta- Alpha- (meta-suifamyl-phenylcarbamyl) betafluoro ethane Para-sultamyl-phenyl-(ethyD-carbamyl chloromethane Meta sulIamyl phenyl -,thiocarbamyl iodo methane Alpha (parasulfamyl phenyl carbamyl) alpha-chloro ethane The present invention. isbased on my discovery that new and valuable materials of particularutility in the plastics and coating arts can be produced by efiectingreaction between ingredients comprising essentially an aldehyde,ineluding polymeric aldehydes, hydroxyaldehydes and aldehyde-additionproducts, and a substituted alkyl halide of the kind embraced by FormulaI. numerous examples of which have been given above. These new reactionproducts are not only valuable in themselves, but find particularutility when incorporated into an acidcuring thermosetting resin, forexample acid-curing thermosetting phenoplasts and aminoplasts. Forinstance, I may add a soluble, fusible aldehyde-reaction product of thesubstituted alkyl halide to an acid-curing thermosetting resin and heatthe resulting mixture. The substituted alkyl halide-aldehyde reactionproduct accelerates the conversion of the acid-curing thermosettingresin to an insoluble, infusible state. Or, I may cause the substitutedalkyl halide itself to react with the acid-curing thermosetting resinand thus accelerate the curing of the resin. Or, I may form a rapidlycuring resin by efiecting reaction between ingredients comprising asubstituted alkyl halide or the kind embraced by Formula I, an aldehyde,including polymeric aldehydes, hydroxyaldehydes and aldehyde-additionproducts, and a phenol (including phenol itself, cresols, xylenols,etc.) or an amino 0r amido compound (including imino and imidocompounds), e. g., aminotriazines, e. g., melamine, aminotriazoles, e.g., guanazole, aminodiazines, e. g. 2,4,6-triamino pyrimidine, a urea,e. g., urea itself, thiourea,'dicya ndiamide, etc.

- The resin syrups and molding compositions of this invention may bestored for long periods of time without material. alteration. In markedcontrast the prior acid curing thermosetting resins, more particularlythose containing direct and pressure and have good plastic flow duringmolding. Hence molded articles of even the most complicated designs canbe made rapidly and economically. The cured compositions have goodcolor, excellent water resistance and surface fin ish and, in general,meet the strength, hardness and other requirements of the particularservice application.

In practicing the present invention the condensation between thevreactants may be carried out under acid, alkaline or neutral conditionsat normal or at elevated temperatures. Any substance or catalyst whichhas an alkaline or an acid nature may be usedto obtain the acid,alkaline or neutral condition, as for example, ammonia, sodiumhydroxide, calcium hydroxide,

ethanol amines, triisopropanol amine, etc.; mixtures of such alkalinesubstances: inorganic or organic acids such as hydrochloric, sulfuric,phosphoric. acetic, acrylic, crotonic, malonic, etc.; mixtures of suchacids; acid salts such as sodium acid sulfate, monosodium phosphate.monosodium phthalate, etc.; basic salts such as ammonium carbonate,potassium carbonate, sodium acetate, etc.; or mixtures of such salts.

I may condense the components used in practicing this invention undervarious conditions. For example, all the components may be mixedtogether and the reaction caused to proceed under acid, alkaline orneutral conditions. Or, I may form an acid-curing thermosetting resin(e. g., an acid-curingpartial condensation product of ingredientscomprisin a phenol and an aldehyde, an acid-curing partial condensationproduct of ingredients comprising an amidogen compound, e. g., melamine,malonic diamide, maleic diamide, urea, thiourea, etc., and an aldehyde),add the substituted alkyl halide thereto and efiect furthercondensation. Or, I may first partially condense the substituted alkylhalide with an aidehyde under acid, alkaline or neutral conditions andthen add thereto at least one other aldehydereactable organic compound,e. g., a Phenol, a urea, aniline, etc., and effect further condensation.Also, I may separately partially condense a substituted alkyl halide ofthe kind embraced by Formula I and a diiierent aldehyde-reactableorganic compound with an aldehyde and then mix the two products ofpartial condensation and eflect further condensation therebetween. Thecomponents of each reaction product may be initially condensed underacid, alkaline or neutral conditions.

Still other ways may be employed in combining the components and inproducing the unmodified and modified condensation products of thisinvention-as readily will be understood by those skilled in the art asthe description of the invention proceeds. These condensation reactionsmay be carried out under a wide variety of time, pressure andtemperature conditions. The temperature of reaction may vary from roomtemperature to the reflux temperature of the reactants at reduced,atmospheric or superatmospheric pressures.

In order that those skilled in the art better may understand how thepresent invention may be carried into efiect, the following illustrativeexamples thereof are given. All parts are by weight.

Example 1 Parts Urea 30.0 Aqueous formaldehyde (approx. 37.1%

HCHO) 64.8 Para sulfamyl phenyl carbamyl chloro methane 0.8 Aqueousammonia (approx. 28% NI-Ia) 4.0

Aqueous solution of sodium hydroxide ture, was produced by molding asample of thedried and ground molding compound for 5 minutes at C. undera pressure of 4,500 pounds per square inch. The molded article had goodwater resistance and the molding compound showedgood plastic flow duringmolding.

Example 2 Parts Melamine 37.8 Aqueous formaldehyde (approx. 37.1%

HCHO) 72.9 Para sulfamyl phenyl carbamyl chloro methane 0.8 Aqueousammonia (approx. 28% NHa).... 1.7

Aqueous solution All of the above ingredients with the exception of thesubstituted alkyl halide were heated together under reflux at theboiling temperature of the mass for 16 minutes. Thepara-suifamylphenyl-carbamyl chloro methane was now added of sodiumhydroxide and the resulting resinous syrup immediately was v Example 3Parts Melamine .373 Thiourea 22.8 Aqueous formaldehyde (approx. 37.1

HCHO) 121.5

Para sulfamyl phenyl carbamyl chloro methane 1.0 Aqueous ammonia(approx. 28% NH3) 3.4 Aqueous solution of sodium hydroxide All of theabove ingredients with the exception of the chloro methane were heatedtogether under reflux at boiling temperature for 15 minutes. The chloromethane was now added and refluxing was continued for an additional 5minutes. A molding compound was prepared by mixing the resultingresinous syrup with 63.5 parts alpha cellulose and 0.3 part zincstearate. The wet molding compound was dried at room temperature untilsuflicient moisture had been removed to provide a material that could bemolded satisfactorily. A well-cured molded piece was produced by moldinga sample of the dried and ground molding compound for 3% minutes at 140C. under a pressure of 4,500 pounds per square inch. The molded articleabsorbed only 0.49% by weight of water when tested for itswater-resistance characteristics as described under Example 2. Themolding compound showed good plastic flow during molding.

Para sulfamyl phenyl carbamyl chloro methane Aqueous ammonia (approx.28% NH3) 3.0 Aqueous solution of sodium hydroxide All of the aboveingredients with the exception of the chloro methane were heatedtogether under reflux at boiling temperature for 2 minutes.

The chloro methane was now'added and refluxing was continued for anadditional 1 minute. The semi-viscous mass produced in this manner wasmixed with 56.5 parts alpha cellulose and 0.3 part zinc stearate. Theresulting wet molding compound was dried at room temperature asdescribed under Example 3. A well-molded product was obtained by moldinga sample of the dried and ground molding compound for 3 minutes at 140C. under a pressure of 4,500 pounds per square inch.

. Example 5 Parts p,'-Bisthioammeline dlethyl ether 17.7 4,6 diaminopyrimidyl 2 para sulfamyl phenyl-carbamyl-methyl sulfide 17.7 Aqueousformaldehyde (approx. 37.1%

.HCHO) a i 40.5 Aqueous solution of sodium hydroxide (0.46 N) Water 50.0

, Para sulfamyl phenyl carbamyl chloro methane, which also may be namedpara- I (chloroacetamiclo) benzene sulfonamide) 0.4

All of the above ingredients with the exception of the.para-sulfamyl-phenyl-carbamyl chloro methane were heated together underreflux at boiling temperature for minutes. Theparasulfamyl-phenyl-carbamyl chloro methane was added to the syrupypartial condensation product and the resulting mixture immediately wasmixed with 42.4 parts alpha cellulose and 0.2 part zinc stearate to forma molding (moldable) composition. The wet molding compound was dried atroom temperature for about 16 hours. A wellcured molded piece having awell-knit and homogeneous structure was produced by molding a sample ofthe dried and ground molding com- 54.9 parts alpha cellulose and 0.3part zinc stearate to form a molding compound. The wet moldingcomposition was dried at 70 C. as described under Example 1. Awell-cured molded piece, having a, well-knit and homogeneous structure,was produced by molding a sample of the dried and ground moldingcompound for 10 minutes at 140 C. under a pressure of 4,500 pounds persquare inch. The molding compound showed goodplastic flow duringmolding.

All of the above ingredients with the exception of the para-sulfamylphenyl-carbamyl chloro methane were heated together under reflux atpound for 4 minutes at 140 C. under a pressure of 3,600 pounds persquare inch.

Example 6 A syrupy phenolic resin was prepared from the followingcomponents:

Parts Phenol 90.0 Aqueous formaldehyde (approx. 37.1%

HCHO) 195.0

Potassium carbonate 2.85

the boiling temperature of the mass for 5 minutes. Thereafter of thetotal amount, that is, 0.6 part, of the chloro methane was added andrefluxing was continued for an additional 9 minutes. At the end of thisreaction period the remainder (0.3 part) of the chloro methane wasadded, followed by refluxing the reaction mass for an additional 5minutes. A molding compound was made from the resulting resinousv syrupby mixing therewith 43.3 parts alpha cellulose and 0.2 part zincstearate. The wet molding composition was dried at room temperature asdescribed under Example 3. A well-cured molded piece was produced bymolding a sample of the dried and ground molding compound for 5 min utesat 140 C. under a pressure of 4,500 pounds per square inch. The moldedarticle had good water resistance, as shown by the fact that it absorbedonly 3.1% by weight of water when tested for its water-resistancecharacteristics as described under Example 2. (The ordinaryureaformaldehyde molding compositions yield molded The above ingredientswere heated together for 4 hours at approximately -'70 C. The clearresinous syrup is referred to in the following formula as syrupyphenolic resin:

Parts Syrupy phenolic resin 60.0 Ure 35.0 Aqueous formaldehyde (approx.37.1%

HCI-IO) 64.8

Para sulfamyl phenyl carbamyl chloro methane 2.0 Aqueous ammonia(approx. 28% NHa) 3.0 Aqueous solution of sodium hydroxide All of theabove ingredients, but using initially only 1 part of thepara-sulfamyl-phenyl-carbamyl chloro methane, were heated together underreflux at boiling temperature .for 30 minutes. At the end of thisreaction period the other 1 part of para-sulfamyl-phenyl-carbamyl chloromethane was added to the reaction mass. which-immediately thereafter wasmixed with gas - Para sulfamyl phenyl carbamyl chloro '.temperature ofthe mass for 5 minutes.

articles which, when similarly tested for water resistance, show awater-absorption value of about 5 to 7%.) The molding compound showedgood flow characteristics during molding.

Ewample 8 Parts Para sulfamyl phenyl carbamyl chloro me 25.0 Aqueoussolution of formaldehyde (approx.

37.1% HCHO) 40.5

are shaken continuously in a flask for 24 hours at room temperature,yielding a soluble, fusible aldehyde-reaction product of thepara-sulfamylphenyl-carbamyi chloro methane that may be used as a curingagent for acid-curing thermosetting resins as described under thepreceding examples.

Example 9 Parts methane Aqueous solution of formaldehyde (approx.

37.1% HCHO) 324 are heated together under reflux at the boiling Theresulting condensation product may be used as a curing agent foracid-curing thermosetting resins as described under Examples 1 to 7,inelusive.

It will be understood. of course, by those skilled in the art that myinvention is not limited to condensation products obtained by reactionof ingradients comprising an aldehyde and the speciflc substituted alkylhalide named in the above illustrative examples. Thus, instead ofparasulfamyl-phenyl-carbamyl chloro methane, I may use ortho sulfamylphenyl carbamyl chloro methane, meta-sulfamyl-phenyl-carbamyl chloromethane, the ortho-, metaor para-sulfamylphenyl-carbamyl bromo methanes,the suliamyltolyl-carbamyi halogeno methanes (e. g., thesuliamyl-tolyl-carbamyl chloro methanes, the sulfamyl-tolyl-carbamylbromo methanes, etc.)

or any other substituted allryl halide (or mixture thereof) embraced byFormula I, numerous specific examples of which have been given herein-.before.

In producing these new condensation products the choice of the aldehydeis dependent largely upon economic considerations and upon theparticular properties desired in the finished product. I prefer to useas the aldehydic reactant formaldehyde or compounds engenderingformaldehyde, e. 9:, paraformaldehyde, hexamethylene tetramine, etc.Illustrative examples of other aldehydes that may be used areacetaldehyde, propionaldehyde, hutyraldehyde, acrolein, methacrolein,crotonaldehyde, benzaldehyde, furfural, hydroxyaldehydes (e. g.,glycollic aldehyde, glyceraldehyde, etc), mixtures thereof, or

mixtures of formaldehyde (or compounds engendering formaldehyde) withsuch aldehydes. Illustrative examples of aldehyde-addition products thatmay be employed instead of the aldchydes themselves are the monoandpoly-(N-carbinol) derivatives, more particularly the monoandpoly-methylol derivatives of urea, thiourea, selenourea and iminourea,monoand poly-(N- carbinol) derivatives of amides of polycarboxylicacids, e. g., maleic, itaconic, fumaric, adipic, malonic, succinic,citric, phthalic, etc., monoand poly-(N-carbinol) derivatives of theaminotriazines, of the aminotriazoles, of the aminodiazines, etc.Particularly good results are obtained with active methylene-containingbodies such as a methylol urea, more particularly monoand dimethylolureas, and a methylol aminotriaaine, e. g., monomethylol melamine andpolymethylol melamines (di-, tri-, tetra-, pentaand hexamethylolmelamines) Mixtures of aldehydes and aldehyde-addition products may beemployed, e. g., mixtures of formaldehyde and methylol compounds such,for instance, as dimethylol urea, trimethylol melamine, hexamethylolmelamine, etc.

The ratio of the aldehydic reactant to the substituted alkyl halide maybe varied over a wide range depending upon the particular propertiesdesired in the final product. Thus, I may use, for example, from 0.5 to6 or '7 or more mols of an aldehyde for each moi of the substitutedalkyl halide. When the aldehyde is available for reaction in the form ofan alkylol derivative, more particularly a methylol derivative such, forinstance. as dimethylol urea, trimethylol melamine, etc., then higheramounts of such aldehyde-addition products ordinarily are used, forexample from 1 to 12,01: or more mols of such alkylol derivatives foreach mol of the substituted alkyl halide.

When the substituted alkyl halide of the kind embraced by Formula I isused primarily as an intercondensable curing reactant for acceleratingthe conversion of acid-curing thermosetting resins to an insoluble,infusible state. only a relatively small amount of such halideordinarily is required, for example an amount corresponding to from 0.2to 0.3% to 3 or 4% by weight of the resin to be cured, calculated on thebasis of the dry resin. In some cases it may be desirable to use higheramounts. for instance up to 7 or 8 or more parts by weight of the halideper parts (net dry) of the acid-curing thermosetting resin. When thesubstituted alkyl halide is incorporated into theacid-curingthermosetting resin in the form of a soluble, fusible aldehyde-reactionproduct thereof, then higher amounts of such reaction product ordinarilyare used as compared with the amount employed when using the substitutedalkyl halide itself.

The substituted alkyl halide or its partial reaction product with analdehyde may be incorporated into the acid-curing thermosetting resineither prior to, during or after the formation of the resin or prior to,during or after the formation of a molding composition containing theacid-curing thermoset-ting resin.

Examples of acid-curing thermosett ng resins, the curing of which isaccelerated by the substituted alkyl halides'herein described or bytheir soluble, fusible aldehyde-reaction products, are the acid-curingphenol-aldehyde resins, aminotriazine-aldehyde resins, e. g.,melamine-formaldehyde resins, aminotriazole-aldehyde resins,urea-aldehyde resins, urea-aminotriazine-aldehyde resins,aminodiazine-aldehyde resins, protein-aldehyde resins, e. g.,casein-formaldehyde resins, resinous condensation products of aldehydessuch as formaldehyde with polyamides as, for instance, malonic diamide,maleic diamide, fumaric diamide, itaconic diamide, etc. Other examplesof amino or amido compounds (amidogen compounds) that may be condensedwith aldehydes such as hereinbei'ore mentioned by way of illustration informing an acid-curing thermosetting resin, more particularly anacid-curing aminoplast, are thiourea, diurea, diethylene triurea, methylurea, acetyl urea, benzoyl urea, phenyl thiourea. asymmetrical diethylurea, allyl urea, 2-chloroal1yl urea, ethylidene urea, guanyl urea,biguanide, aminoguanidine, melamine. triureido melamine, ammeline,ammelide, melem, melam, melon, aminotriazoles, amlnodiazines, etc.Suitable mixtures of such compounds also may be used.

Phenol itself and various substituted phenols, for example the cresols,the xylenols, etc., may be condensed with aldehydes, e. g.,formaldehyde, furfural, etc., to form acid-cutting thermosetting resinsof the phenoplast type, and these thermosetting resins then can be curedto the insoluble and infusible state with the aid of the hereindescribedsubstituted alkyl hal des or with the soluble, fusible aldehyde-reactionproducts of such halides.

If desired, the fundamental reaction products of this invention may bemodified by introducing other bodies before, during or aftercondensation between the primary components. Numerous examples ofmodifying agents that may be employed are given, for instance, inDAlelio and Holmes Patent No. 2,265,688, issued December 9, 1941, page3, column 2, lines 53-75, page 4, column 1, lines 1-40, which patent isassigned to the same assignee as the present invention.

Thermosetting molding compositions comprisiarly at temperatures of theorder of 100 6 ing a filler and an acid-curing thermomttingreaincarryingacnringagentcomprisingasubstituted alkyl halide of the kindhereindescribed, or a soluble; fusible aldehyde-reaction product of sucha halide, may be molded into a varietyofshapesunderheatandpressuremorepartl to 200' 0., preferably fromapproximately 120 C. to 180 C. The molding compositions show goodplastic flow during molding, since the curing agent not only functionsas such but also generally serves to impart improved plastic flow to themolding composition. Molded articles of manufacture comprising themolded, heat-hardened molding compositions of this invent on have a goodsurface finish, show no evidence of bleeding" the curing agent, are wellcured throughout, and show no loss in any of their other usefulproperties due to the presence of the here indescribed substitutedallryl halide or aldehyde-reaction product thereof.

whatlclaimasnewanddesiretosecureby Letters Patent of the United Statesis:

1. A composition comprising an acid-curing, thermosetting resin carryinga curing agent therefor, comprising a compound selected from the classconsisting of (1) compounds represented by the general formula where nrepresents an integer and is at least 1 and not more than 2, Zrepresents a member of the class consisting of oxygen and sulfur, Yrepresents a divalent carbocyclic radical, Rrepresentsamemberoftheclessconsistingofhydrogen and monovalenthydrocarbon and haloradicals, andxrepresents a halogen I atom; and (2)soluble, fusible aldehyde-reaction products of the compounds of (1).

2. A composition comprising an acid-curing, thermosetting.phenol-aldehyde resin having in corporsfed therein a compoundrepresented by the general formula where n represents an integer and isat least 1 and not more than 2, Z represents a member oftheclassconsistingofoxygenandsulfur,Yrepresents a divalent carbocyclicradical, R represents a member of the class consisting of hydrogen andmonovalent hydrocarbon and halohydrocarbon radicals, and X represents ahalogen atom.

3. A composition comprising an acid-curing, thermosetting,amidogen-aldehyde resin having incorporated therein a. compoimdrepresented by the general formula Z RHNSOr-Y-diB--C-Bux assesswherenrepresentsanintegerandisatleastl and not more than 2, Z representsa member of the class consisting of oxygen and sulfur, Y represents adivalent carbocyclic radical, R reprecents a member of the classconsisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbonradicals, and X represents a halogen atom.

5. A composition as in claim 4 wherein the aldehyde is formaldehyde.

6. A composition comprising the product of reaction of ingredientscomprising a phenol, an aldehyde and a compound reprwented by thegeneral formula where n represents an integer and is at least 1 and notmore than 2, Z represents a member of the class consisting of oxygen andsulfur, Y rep resents a divalent carbocyclic radical, R represenis amember of the class consisting of hydrogen and monovalent hydrocarbonand halo-hydrocarbon radicals. and X represents a halogen atom.

'l. A composition comprising the product of reaction of ingredientscomprising a urea, an aldehyde and a compound represented by the eneralformula I ma Or-Y-NR-Zl-C-Ba-X wherenrepresentsanintegerandisatleastland not more than 2, Z represents a memberoftheclassccnslstingofoxygenandsulfimY represents a divalent cerbocyclicradical, R represents a member of the class consisting'of hydrogen andmonovalent hydrocarbon and halohydrocarbon radicals, and X represents ahalogen atom.

8. A composition comprising the product of reaction of ingredientscomprising an aminotriaaine, an aldehyde and a compound represented bythe general formula Z BEN 8 Or-Y-NB--C-M' where n representsan integerand is at least 1 and not more than 2, Z represents a member oftheelassconsisting'ofoxygenandsulfunYrepresents a divalent carbocyclicradical, R representsamemberoftheclassconsistingofhydrogen andmonovalent hydrocarbon and halohydrocarbon radicals. and x represents ahalogen atom.

9. A heat-curable resinous condensation product of ingredientscomprising urea, formaldehyde and a compound represented by the generalformula melamine, formaldehyde and a compoimd rep resented by thegeneral formula product of reaction of (1) a partial condensationproduct of ingredients comprising a phenol and I an aldehyde, and (2) acompound represented by the general formula where Y represents adivalent carbocyclic radical.

13. A composition comprising the resinous product of reaction or 1) apartial condensation product of ingredients comprising a urea and analdehyde, and (2) a compound represented by the general formula where Yrepresents a divalent carbocyclic radical.

14. A resinous composition comprising the product of reaction of (1) apartial condensation product obtained by reaction, while admixed with analkaline substance, of ingredients comprising urea and formaldehyde, and(2) a sulfamylphenyl-carbamyl chloro methane.

15. A composition comprising the resinous product of reaction of (1) apartial condensation product obtained by reaction, while admixed with analkaline substance, of ingredients comprising urea and formaldehyde, and(2) a sulfamyl-tolylcarbamyl chloro methane.

16. A resinous composition comprising the product of reaction of (l) apartial condensation product obtained by reaction, while admixed with analkaline substance, of ingredients comprising melamine and formaldehyde,and (2) a sulfamylchloro methane.

phenyl-carbamyl comprising the resinous 17. A composition product ofreaction of ingredients comprising urea, formaldehyde andpara-sulfamyl-phenylcarbamyl chloro methane.

18. A thermosetting molding composition comprising a illlerand anacid-curing partial condensation product of ingredients comprising ureaand formaldehyde, said condensation product having incorporated thereina small amount of a curing agent comprising a sulfamyl-phenylcarbamylchloro methane.

19. The method of preparing new condensation products which compriseseflectlng reaction between ingredients comprising an aldehyde and acompound represented by the general formula where n represents aninteger and is at least 1 and not more than 2, Z represents a member ofthe class consisting of oxygen and sulfur, Y represents a divalentcarbocyclic radical, It represents a member of the class consisting ofhydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, and Xrepresents a halogen atom.

20. The method which comprises eiIecting partial reaction betweeningredients comprising urea and formaldehyde under alkaline conditions,adding to the resulting partial condensation product a small amoimt of asulfamyl-phenyl-carbamyl chloro methane, and causing the said chloromethane to inter-condense with the said partial condensation product.

GAETANO F. DALELIO.

CERTIFIQATE 0F CORRECTION. Patent No. 2,3 7,655. Septenber 5, 19b1,.

ammo F. D ALELIO.

It is hereby certified that error appears in the printed specificationof the aboire mmbered patent requiring correctionas follows: Page 1,sec- .ond co1umn,- line 16, after -"e.g. strike out '67-"; line 25,after "9.1-

koxy insert acomma; line 59, after "effecting" strike out "a"; sameline, after "between" insert --a--; page 1 first column, line 27-, after'sulfonamide" strike out the parenthesis; page 5, second column, line 7,for "0.2 to" read --0.2 or--; line 58, for "acid-cutting read--acid-curing--; page 6, second column, line 62, claim 9, for thatportion of the formula reading "C R X" read --C H X--; and that the saidI-etters Patent should be read with this correction therein that thesame may conformto the rec- 0rd of the case in the Patent Office.

Signed and sealed this 7th da of November, A. D. 19%.

Leslie Frazer (Seal) Acting Comniissioner of Patents.

